CN109200824A - A kind of preparation method of nascent state in-situ modification reverse osmosis membrane - Google Patents
A kind of preparation method of nascent state in-situ modification reverse osmosis membrane Download PDFInfo
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- CN109200824A CN109200824A CN201811234418.3A CN201811234418A CN109200824A CN 109200824 A CN109200824 A CN 109200824A CN 201811234418 A CN201811234418 A CN 201811234418A CN 109200824 A CN109200824 A CN 109200824A
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- reverse osmosis
- nascent state
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- organic phase
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- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000004048 modification Effects 0.000 title claims abstract description 16
- 238000012986 modification Methods 0.000 title claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 13
- 239000012074 organic phase Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008346 aqueous phase Substances 0.000 claims abstract description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 12
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 12
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 7
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000006011 modification reaction Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 235000002639 sodium chloride Nutrition 0.000 description 16
- 229960002668 sodium chloride Drugs 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 15
- 230000004907 flux Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- KILYNHHCRKVDRU-UHFFFAOYSA-N [S].C1CC2(C)C(=O)CC1C2(C)C Chemical compound [S].C1CC2(C)C(=O)CC1C2(C)C KILYNHHCRKVDRU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation methods of nascent state in-situ modification reverse osmosis membrane, and polynary acyl chlorides is added in alkane solvent and stirs into homogeneous and transparent organic phase, sealing and standing；Aqueous phase solution is made in polyamine dissolution, adjusts pH to 10；Aqueous phase solution containing polyamine is poured on porous support membrane and is stood, extra aqueous phase solution is then outwelled, it is water stain to what is be visible by naked eyes to drain film surface；It is subsequently poured into the organic phase solution containing polynary acyl chlorides, nascent state film is formed, then pours into the polynary acyl chlorides organic phase solution modification reaction containing various concentration again；Nascent state reverse osmosis membrane after modification is put into baking oven and dries film forming.The present invention reduces nascent state film defect by the degree of cross linking on regulation nascent state reverse osmosis membrane surface, regulates and controls nascent state film surface charge, effectively enhances the differential permeability of reverse osmosis membrane.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecule organic film, in particular to a kind of nascent state in-situ modification are reverse osmosis
The preparation method of film.
Background technique
Reverse osmosis technology is a kind of low energy consumption, efficient environmentally protective isolation technics, has simple process, operating condition
Mildly, the features such as separative efficiency is high achieves in the fields such as bitter and sea water desalination, wastewater treatment and is widely applied.
The core of reverse osmosis separation technology is reverse osmosis membrane, and aromatic polyamides reverse osmosis composite membrane accounts for market predominantly
Position.Aromatic polyamides reverse osmosis composite membrane is that one layer of ultra-thin polyamide functional layer is combined to aperture by interfacial polycondensation is appropriate
Open support film surface, interfacial polycondensation combination process determine that we can regulate and control its each layer and reach optimal separation
Energy.Porous support membrane can achieve optimal intensity and resistance to pressure, and ultra-thin aramid layer can be optimized to ideal selected area update strategy
Property.
Permeation flux and salt rejection rate are to evaluate two important parameters of reverse osmosis membrane.High throughput, high desalination reverse osmosis membrane are
The need of industrial application at present are at present concentrated mainly on the improvement of reverse osmosis membrane and research and develop new reaction monomers, film surface coating changes
Property and addition inorganic nanoparticles improve reverse osmosis membrane differential permeability.It, cannot be from although achieving certain effect
It fundamentally solves the problems, such as, and new monomer research and development are difficult and at high cost, surface is modified and addition nano particle is easy to fall off, and meeting
Secondary pollution is caused to environment.Only a few people regulates and controls ultra-thin polyamides it may be noted that by reverse osmosis membrane nascent state in-situ modification
Amine functions layer enhances the differential permeability of reverse osmosis composite membrane.This is a kind of new knowledge to reverse osmosis membrane film forming procedure.
Summary of the invention
The present invention is insufficient for current reverse osmosis composite membrane film forming procedure understanding, and it is reverse osmosis to propose nascent state in-situ modification
The preparation method of film can effectively enhance the differential permeability of reverse osmosis composite membrane.
The technical problem to be solved in the invention is to pass through regulation nascent state reverse osmosis membrane surface polyamine and polynary acyl chlorides
Ratio, improve the degree of cross linking, reduce nascent state film defect, regulate and control film surface charge, thus effectively enhance reverse osmosis membrane selection
Permeability.
The present invention is achieved by the following technical programs: a kind of preparation method of nascent state in-situ modification reverse osmosis membrane,
Its feature the following steps are included:
(1) by mass volume ratio score be 0.005-0.3% polynary acyl chlorides be added in alkane solvent stir into it is uniform
Transparent organic phase, sealing and standing 2 hours or more；
(2) aqueous phase solution is made in the polyamine dissolution that mass volume ratio score is 1.0-3.0%, adjusts pH to 10；
(3) aqueous phase solution containing polyamine is poured on porous support membrane and stands 1-5 minutes, then outwell extra water
It is water stain to what is be visible by naked eyes to drain film surface for phase solution；
(4) it is subsequently poured into the organic phase solution containing polynary acyl chlorides, 10-30 seconds formation nascent state films is reacted, then falls again
Enter polynary acyl chlorides organic phase solution modification reaction 10-60 seconds containing various concentration；
(5) the nascent state reverse osmosis membrane after modification is put into 60-90 DEG C of baking oven to dry 5-10 minutes and is formed a film.
Preferably, alkane solvent described in above-mentioned preparation method is n-hexane, in hexamethylene, normal heptane, petroleum ether
One or more.
Preferably, polyamine described in above-mentioned preparation method is m-phenylene diamine (MPD), polynary acyl chlorides is pyromellitic trimethylsilyl chloride.
Preferably, the reagent that pH is used is adjusted described in above-mentioned preparation method as triethylamine and camphorsulfonic acid, wherein
Camphorsulfonic acid quality volume fraction is 1.0-5.0%.
Preferably, porous support membrane described in above-mentioned preparation method is the polysulfones ultrafiltration of molecular cut off 3~50,000
Film.
The utility model has the advantages that the degree of cross linking of the present invention by regulation nascent state reverse osmosis membrane surface, reduces nascent state film defect, adjust
Nascent state film surface charge is controlled, the differential permeability of reverse osmosis membrane is effectively enhanced.It can effectively be mentioned in the case where retention loss is small
The flux of high bitter reverse osmosis membrane.The rejection of sea water desalination membrane can be effectively improved in the case where throughput loss is small.And
Not introducing third party's additive reduces cost, reduces the potential danger to environment, and simple process is easy to industrialize.
Specific embodiment
Combined with specific embodiments below, technical solution of the present invention is further elaborated with.
The test operation condition used in the present invention are as follows: the sodium-chloride water solution of 2000ppm, operating pressure 1.55MPa,
Operation temperature is 25 DEG C, the sodium-chloride water solution of pH=8 and 32000ppm, operating pressure 5.5Mpa, operation temperature 25
DEG C, pH=8.Following embodiment provides the preparation explanation and their differential permeability of reverse osmosis membrane.However, these embodiments
Only it is to provide explanation rather than limits the present invention.
Embodiment 1
Pyromellitic trimethylsilyl chloride is added in n-hexane and is stirred and dissolved into homogeneous and transparent organic phase, mass volume ratio score
For 0.1% and 0.01%.It is 2.0% (triethylamine and camphor sulphur that aqueous phase solution quality volume fraction, which is made, in m-phenylene diamine (MPD) dissolution
Acid for adjusting pH=10, wherein 4.0%) camphorsulfonic acid mass volume ratio score is.Aqueous phase solution is poured on polysulfones support membrane, it is quiet
Only 5 minutes, extra water phase is then removed, drains to film surface and is visible by naked eyes water stain, then pour into the equal benzene containing 0.1%
Three formyl chloride organic phases react 30s, then outwell organic phase and form nascent state reverse osmosis membrane, then pour into the equal benzene containing 0.01%
Three formyl chloride organic phase solution in-situ modifications react 30s, then outwell organic phase, are finally putting into drying in baking oven and form a film (at heat
80 DEG C of temperature of reason, 10 minutes time).
Under 1.55MPa pressure, the sodium-chloride water solution of 2000ppm is tested, the permeation flux of diaphragm is 59.5 (L m- 2h-1), the rejection to sodium chloride is 99.71%.
Embodiment 2
Pyromellitic trimethylsilyl chloride is added in hexamethylene and is stirred and dissolved into homogeneous and transparent organic phase, mass volume ratio score
It is 0.1%.It is 2.0% (triethylamine and camphorsulfonic acid adjusting pH that aqueous phase solution quality volume fraction, which is made, in m-phenylene diamine (MPD) dissolution
=10, wherein 4.0%) camphorsulfonic acid mass volume ratio score is.Aqueous phase solution is poured on polysulfones support membrane, static 5 minutes,
Then extra aqueous phase solution is removed, drains to film surface and is visible by naked eyes water stain, then pour into the equal benzene front three containing 0.1%
Then the organic phase reaction 30s of acyl chlorides outwells organic phase and forms nascent state reverse osmosis membrane, then pours into having without pyromellitic trimethylsilyl chloride
Machine phase cyclohexane solution in-situ modification reacts 30s, then outwells organic phase, after be put into baking oven drying film forming (heat treatment temperature
80 DEG C, 10 minutes time).
Under 1.55MPa pressure, the sodium-chloride water solution of 2000ppm is tested, the permeation flux of diaphragm is 64.98 (L
m-2h-1), the rejection to sodium chloride is 99.64%.
Embodiment 3
Film modified without nascent state, remaining operating procedure is same as Example 1.It is right under 1.55MPa pressure
The sodium-chloride water solution of 2000ppm is tested, and the permeation flux of diaphragm is 45.32 (L m-2h-1), the rejection to sodium chloride is
99.77%.Under 5.5MPa pressure, the sodium-chloride water solution of 32000ppm is tested, the permeation flux of diaphragm is 69.22 (L
m-2h-1), the rejection to sodium chloride is 99.03%.
Embodiment 4-8
Change the concentration of pyromellitic trimethylsilyl chloride in organic phase solution during in-situ modification, other steps and 1 phase of embodiment
Same operating method, prepared composite membrane are tested the sodium-chloride water solution of 2000ppm, are obtained under 1.55MPa pressure
As a result as shown in the table:
Embodiment 9
Pyromellitic trimethylsilyl chloride is added in n-hexane and is stirred and dissolved into homogeneous and transparent organic phase, mass volume ratio score
For 0.1% and 0.06%.It is 2.0% (triethylamine and camphor sulphur that aqueous phase solution quality volume fraction, which is made, in m-phenylene diamine (MPD) dissolution
Acid for adjusting pH=10, wherein 4.0%) camphorsulfonic acid mass volume ratio score is.Aqueous phase solution is poured on polysulfones support membrane, it is quiet
Only 5 minutes, extra water phase is then removed, drains to film surface and is visible by naked eyes water stain, then pour into the equal benzene containing 0.1%
Three formyl chloride organic phases react 30s, then outwell organic phase and form nascent state reverse osmosis membrane, then pour into the equal benzene containing 0.06%
Three formyl chloride organic phase solution in-situ modifications react 30s, then outwell organic phase, are finally putting into drying in baking oven and form a film (at heat
80 DEG C of temperature of reason, 10 minutes time).
Under 5.5MPa pressure, the sodium-chloride water solution of 32000ppm is tested, the permeation flux of diaphragm is 65.92 (L
m-2h-1), the rejection to sodium chloride is 99.32%.
Embodiment 10
Pyromellitic trimethylsilyl chloride is added in hexamethylene and is stirred and dissolved into homogeneous and transparent organic phase, mass volume ratio score
For 0.1% and 0.04%.It is 2.0% (triethylamine and camphor sulphur that aqueous phase solution quality volume fraction, which is made, in m-phenylene diamine (MPD) dissolution
Acid for adjusting pH=10, wherein 4.0%) camphorsulfonic acid mass volume ratio score is.Aqueous phase solution is poured on polysulfones support membrane, it is quiet
Only 5 minutes, extra water phase is then removed, drains to film surface and is visible by naked eyes water stain, then pour into the equal benzene containing 0.1%
Three formyl chloride organic phases react 30s, then outwell organic phase and form nascent state reverse osmosis membrane, then pour into the equal benzene containing 0.04%
Three formyl chloride organic phase solution modification reaction 30s, then outwell organic phase, are finally putting into drying film forming (heat treatment temperature in baking oven
80 DEG C of degree, 10 minutes time).
Under 5.5MPa pressure, the sodium-chloride water solution of 32000ppm is tested, the permeation flux of diaphragm is 67.81 (L
m-2h-1), the rejection to sodium chloride is 99.22%.
Claims (5)
1. a kind of preparation method of nascent state in-situ modification reverse osmosis membrane, it is characterised in that: the following steps are included:
(1) the polynary acyl chlorides that mass volume ratio score is 0.005-0.3% is added in alkane solvent and stirs into transparent and homogeneous
Organic phase, sealing and standing 2 hours or more；
(2) aqueous phase solution is made in the polyamine dissolution that mass volume ratio score is 1.0-3.0%, adjusts pH to 10；
(3) aqueous phase solution containing polyamine is poured on porous support membrane and stands 1-5 minutes, it is molten then to outwell extra water phase
It is water stain to what is be visible by naked eyes to drain film surface for liquid；
(4) it is subsequently poured into the organic phase solution containing polynary acyl chlorides, 10-30 seconds formation nascent state films is reacted, then pours into and contain again
There is the polynary acyl chlorides organic phase solution in-situ modification of various concentration to react 10-60 seconds；
(5) the nascent state reverse osmosis membrane after modification is put into 60-90 DEG C of baking oven to dry 5-10 minutes and is formed a film.
2. preparation method according to claim 1, it is characterised in that: the alkane solvent is n-hexane, hexamethylene, just
One of heptane, petroleum ether are a variety of.
3. preparation method according to claim 1, it is characterised in that: the polyamine is m-phenylene diamine (MPD), piperazine, fat
One or more in diamines, polynary acyl chlorides is pyromellitic trimethylsilyl chloride.
4. preparation method according to claim 1, it is characterised in that: the reagent that the adjusting pH is used be triethylamine and
Camphorsulfonic acid, wherein camphorsulfonic acid quality volume fraction is 1.0-5.0%.
5. according to preparation method described in patent requirements 1, it is characterised in that the porous support membrane is molecular cut off 3~5
Ten thousand polysulfone ultrafiltration membrane.
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| CN201811234418.3A CN109200824A (en) | 2018-10-23 | 2018-10-23 | A kind of preparation method of nascent state in-situ modification reverse osmosis membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973462A (en) * | 2021-03-24 | 2021-06-18 | 浙江工业大学 | Preparation method of high-selectivity reverse osmosis membrane by covering membrane surface defects |
| CN114146572A (en) * | 2021-12-07 | 2022-03-08 | 天津大学 | Preparation method of amide segment embedded covalent organic framework composite membrane and filter membrane thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973462A (en) * | 2021-03-24 | 2021-06-18 | 浙江工业大学 | Preparation method of high-selectivity reverse osmosis membrane by covering membrane surface defects |
| CN114146572A (en) * | 2021-12-07 | 2022-03-08 | 天津大学 | Preparation method of amide segment embedded covalent organic framework composite membrane and filter membrane thereof |
| CN114146572B (en) * | 2021-12-07 | 2023-06-30 | 天津大学 | Preparation method of amide chain segment embedded covalent organic framework composite membrane and filter membrane thereof |
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